Polynitroamine salts



. invention in any way.

1 States Patent POLYNITROAMINE SALTS Milton B. Frankel, Pasadena, Calif., assignor to'Aerojet-i i General Co'rpmation, Azusa, Calif a" corporation at Ohio No Drawing. Application October 29, 1957 SeriafNo. 694,695

20 Claims. (Cl. 260-583) This invention relates to. new compositions of matter and a method fortheir preparation. In particular, this invention relates to bis-inorganic acid salts of gem-dinitro.

diamines having the generalformula:

wherein X is a nitrate or perchlorate radical and A and A are alkylene radicals which can be the same or different. a

't th ir high oxygen content, the gem-'dinitro' salt compounds of this invention are usefulas propellant I additives, They also have utility as high explosives'and can be used in any, conventional explosive missile, proeans;raareeorthe' like 'asthe main explosive charge.

An example of such'a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One way diffusing the high explosives in'a device such as that disclosedin UnitedStates Patent No.1 2,470,162 is to pack the crystalline explosive in powder form into the war Head of themissile'. Alternatively, the crystals can be first pelletized and then packed, A' charge thus prepared 'is siifiicielnt ly f insens itiv'e to withstand the shock entailed in theejection-of a'shell from a gun barrel'or from a rocket launching tube under the pressure developed from ignition'of a propellant charge, and can be caused to explode on operation of an impact or time-fuse mechanism firing a detonating explosive such as leadazide or mercury fulminate.

The" compounds of this invention are preparedby reacting a gem-dinitro diisocyanate, with dilute nitric or perchloric acid, in accordance with the general reaction scheme set forth below:

wherein X, A and A are as defined above.

To more clearly illustrate my invention, the following example is presented. It is to be understood, however, that this example is presented merely as a means of illustrati on and is not intended to limit the scope of the EXAMPLE Preparation of the"nitric acid salt of 3,3-dinitr-L5- pentane diamine 'Inaround bottom flask fitted with, a reflux condenser,

' ,3,3-dinitro 1,5 pentane diisocyanate was heated with a tenl'fold excess of 35% nitric acid onja steam bath "for aperiod of 3 hours. The solution'wa's evaporated to dryness in vacuo "leaving a quantitative yield of the hisnitric acid salt of 3,3-dinitro l,5-pentane diamine. Upon recrystallization from methanol, the product exhibited a melting point of 151153 C. The elemental analysis 0 the product is as follows:

Calculated for C H N O percent C, 18.87; percent H, 4.43; percent N, 26.41. Hound: percent C, 19.07; percent H, 4.70; percent N, 26.22.

The explosive power of this compound was calculated to be:

Lead block value, 120 T.N.T.=100 Ballistic mortar value, 130-; T .N.T.=100

As indicated above, a dilute acid is employed for the reaction of the present invention. By dilute acid, as the term is employed herein, is meant an aqueous solution of acid, preferably of from about 3 0 to'about 85% concentration. The reaction of this invention is a vigorous one and I have found that optimum control can be exercised when anacid of about35%"concentration is employed in excess. The excess acid acts as adiluent or solvent and thereby effects moderation of the reaction.

Reaction temperature is not critical in the practice. of this invention, the only effect of temperature variasuch as sodium azide, and subsequently heating under' anhydrous conditions to effect rearrangementto the desired diisocyanate, as more fully disclosed inassignees copending US. patent application Serial No. 623,728, filed November 16, 1956.

ilt will be appreciated that a; wide variety: of bisinorganic acid salts of gem-d ni dia n s a b are pared in accordance with the method of my invention. For example, 4,4-dinitro 1,7-heptane diisocyanate and 4,4-dinitro-1,8-cctane diisocyanate react with dilute nitric acid to produce the bis-nitric acid salts of the correspending diamines, namely, 4-4-dinitro-1,7-he ptane diamine and 4,4-dinitro-1,8-octane diamine. Similarly, 3,3-dinitro-1,5-pentane diisocyanate and 5 ,5-dinitro-l',9- nonane diisocyanate react with dilute perchloric' acid .to yield the bis-perchloricacid salts of the corresponding diamines, namely, 3,3-dinitro-1,5-pentane diamine and 5,5 -dinitro-1,9-nonane diamine.

It is apparent thatany number of my series of novel compounds can be obtained by reacting the appropriate starting materials as taught herein.

This application is a continuation-in-part of my co- 7 pending US. patent application Serial. No. 412,103, filed February 23, 1954.

I claim:

1. As new compositionsuofmatter, the bis-inorganic acid salts of gem-dinitro diamines having the, general formula:

wherein X is a radical selected fromthe groupconsisting of nitrate and perchloraterradicals and A and A are lower alkylene radicals.

' Patented Apr.- ZIG, 1 96.0

2. As new compositions of matter, the his-nitric acid salts of gem-dinitro diamines having the general formula:

wherein A and A are lower alkylene radicals.

3. As new compositions of matter, the bis-perchloric acid salts of gem-dinitro diamines having the general formula:

wherein A and A are lower alkylene radicals.

4. As a new composition of matter, the bis-nitric acid salt of 3,3-dinitro-1,5-pentane diamine having the structural formula:

5. As a new composition of matter, the bis-nitric acid salt of 4,4-dinitro-1,7-heptane diamine having the structural formula:

6. As a new composition of matter, the bis-nitric acid salt of 4,4-dinitro-1,8-octane diamine having the structural formula:

7. As a new composition of matter, the bis-perchloric acid salt of 3,3-dinitro-l,5-pentane diamine having the structural formula:

8. As a new composition of matter, the bis-perchloric acid salt of 5,5-dinitro-l,9-nonane diamine having the structural formula:

9. The method of preparing bis-inorganic acid salts of gem-dinitro diamines having the general formula:

ITIO:

N02 which comprises reacting a gem-dinitro diisocyanate having the general formula:

with a dilute inorganic acid having the general formula HX; wherein X is a radical selected from the group consisting of nitrate and perchlorate radicals and A and A are lower alkylene radicals.

10. The method of preparing bis-nitric acid salts of gem-dinitro diamines having the general formula:

ITTO:

which comprises reacting a gern-dinitro diisocyanate having the general formula:

11. The method of preparing bis-perchloric acid salts of gem-dinitro diamines having the general formula:

which comprises reacting a gem-dinitro diisocyanate having the general formula:

with dilute perchloric acid; wherein A and A are lower alkylene radicals.

12. The method of preparing the bis-nitric acid salt of 3,3-dinitro-l,5-pentane diamine, which comprises reacting 3,3-dinitro-l,5-pentane diisocyanate with dilute nitric acid.

13. The method of preparing the bis-nitric acid salt of 4,4-dinito-l,7-heptane diamine which comprises reacting 4,4-dinitro-l,7-heptane diisocyanate With dilute nitric acid.

14. The method of preparing the bis-nitric acid salt of 4,4-dinitro-l,8-octane diamine, which comprises reacting 4,4-dinitro-l,8-octane diisocyanate with dilute nitric acid.

15. The method of claim 9 in which the dilute inorganic acid has a concentration of from about 30% to about 16. The method of claim 10 in which the dilute nitric acid has a concentration of about 35%.

17. The method of preparing the bis-nitric acid salts of gem-dinitro diamines having the general formula:

which comprises reacting a gem-dinitro diisocyanate having the general formula:

lTIO:

with 35% nitric acid, in the presence of excess dilute nitric acid and at an elevated temperature; wherein A and A are lower alkylene radicals.

18. The method of preparing the bis-nitric acid salts of gem-dinitro diamines having the general formula:

which comprises reacting a gem-dinitro diisocyanate having the general formula: a

with 35% nitric acid, in the presence of dilute nitric acid and at a temperature of about (3.; wherein A and A are lower alkylene radicals.

19. The method of preparing thehis-perchloric acid salt of 3,3-dinitro-l,5-pentane diamine, which comprises reacting 3,3-dinitro-1,5-pentane diisocyanate with dilute perchloric acid.

20. The method of preparing the bis-perchloric acid salt of 5,5-dinitro-1,9-nonane diamine, which comprises reacting 5,5-dinitro-1,9-nonane diisocyanate, with dilute perchloric acid.

6 7 References Cited in the file of this patent Feiser et al.: "Organic Chemistry, 1944, D. C. Heath and Co., Boston, page 233.

Wertheim: Textbook of Organic Chemistry," 2nd ed., The Blakiston Co., Philadelphia (1946), pp. 308-309.

Herzog et al.: American Chemical Society-Abstracts of Papers, 118th meeting, 1950, p. 25N. 

1. AS NEW COMPOSITIONS OF MATTER, THE BIS- INORGANIC ACID SALTS OF GEM- DINITRO DIAMINES HAVING THE GENERAL FORMULA 